Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen

Definitions

• This invention relates to a process for the preparation of copolymers of monoallylamine and diallylamine derivatives.
• Monoallylamine is hardly polymerized with an ordinary radical initiator, and regarding such polymerization of monoallylamine, there are available only a few reports including a method in which radiation polymerization is carried out by the use of gamma rays in a protonic acid (such as phosphoric acid, sulfuric acid or hydrochloric acid) (V.A. Kabanov et al, Vysokomol. Soed., 18, No. 9, 1957-1962, 1967, and 18, No.-10, 2233-2238, 1976).
• a protonic acid such as phosphoric acid, sulfuric acid or hydrochloric acid
• Polymonoallylamine is a very interesting type of polymer for practical use. Though monoallylamine has been industrially produced since long, no attempt has ever been made for the industrial production of polymonoallylamine which is a polymer of monoallylamine. The same is the case with the diallylamine derivatives. Except for the quaternary ammonium salt type diallylamine derivative monomers such as dimethyldiallylammonium chloride, there are known few past attempts for the industrial production of the derivatives of secondary amines such as diallylamine and tertiary amines such as methyldiallylamine.
• the present invention has for its object to provide an industrially excellent process for the high-yield production of a copolymer with a high degree of polymerization from monoallylamine and a diallylamine derivative by using a radical initiator.
• the present inventors have made extensive researches for a process capable of the high-yield production of the copolymer with a high degree of polymerization by conducting a radical polymerization of monoallylamine and a diallylamine derivative, both of which are poor in polymerizability as mentioned above, under the conditions which are easy of industrial practice.
• the copolymer obtained according to the process of this invention is supposed to have the following structural formula (2) or (3): (wherein R 1 , R 2 , R 3 , R 4 and X are as defined above, and i, m and n are each a positive integer showing the degree of polymerization).
• diallylamine derivatives represented by the general formula (1) are shown below:
• the preferred examples of the inorganic acid salts of monoallylamine used in this invention are hydrochloride, sulfate, nitrate and phosphate.
• Such inorganic acid salt of monoallylamine is first dissolved in a solvent with a monomer of the general formula (1).
• a solvent used as the solvent in this invention is a polar solvent, that is, water, an aqueous solution of an inorganic acid (such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), an organic acid (such as formic acid, acetic acid, propionic acid, etc.) or an aqueous solution thereof, alcohol, dimethyl sulfoxide, dimethylformamide and the like.
• the initiator used as catalyst in this invention is a radical initiator containing an azo group and a group having cationic nitrogen atom in the molecule, but in view of easiness of synthesis, there are preferably used the inorganic or organic acid salts such as hydrochloride, sulfate, phosphate, alkylsulfate, para-toleuenesulfonate, formate, acetate and propionate of azo compounds represented by the following general formula (4): (wherein at least one, preferably both of R 5 and R 6 are a group containing cationizable nitrogen atom selected form the group consisting of aminoalkyl, aminoaryl, amidinylalkyl, amidinylaryl, aminoalkaryl, aminoaralkyl, amidinylaralkyl, amidinylalkaryl, cyanoaminoalkyl and cyanoaminoalkaryl, and in case only one of R 5 and R 6 is a group containing cationi
• the especially desirable ones are those having secondary or tertiary carbon atom adjacent to the azo group.
• the typical examples of such compounds are: 2,2'- diamidinyl-2,2'-azopropane hydrochloride, 2,2'-diamidinyl-2,2'-azobutane hydrochloride, 2,2'-diamidinyl-2,2'-azopentane hydrochloride, 2,2'-bis-(N-phenylamidinyl)-2,2'-azopropane hydrochloride, 2,2'-bis-(N-phenylamidinyl)-2,2'-azopropane hydrochloride, 2,2'-bis-(N-phenylamidinyl)-2,2'-azobutane hydrochloride, 2,2'-bis-(N,N-dimethylamidinyl-2,2'-azopropane hydrochloride, 2,2'-bis-(N,N-dimethylamidinyl-2,2'-
• 2,2'-azobis-(2-methyl-4-diethylamino)-butylo- nitrile hydrochloride 2,2'-azobis-(2-methyl-4-dimethyl- amino)-butylonitrile hydrochloride, 2,2'-azobis-(2-methyl-4-diethylamino)-butylonitrile hydrochloride, quaternary ammonium salt type azonitrile obtained by quaternarizing 2,2'-azobis-(2-methyl-4-diethylamino)-4-butylonitrile or 2,2'-azobis-(2-methyl-4-dimethylamino)-butylonitrile with dimethylsulfuric acid or methyl p-toluenesulfonate.
• Said radical initiators containing an azo group and a group having cationic nitrogen atom are the known compounds, and their preparation processes and the examples of polymerization of unsaturated compounds by using these initiators are disclosed in U.S. Patent Nos. 2,599,299, 2,599,300, 2,605,260 and 2,744,105.
• the unsaturated compounds to be polymerized are the ones (such as ethylene, acrylonitrile, chlorobutadiene, etc.) which are different in chemical structure from monoallylamine and diallylamine derivatives used in the present invention. Therefore, these disclosures are not allusive to the inventive substance of the present invention.
• the amount of the initiator added varies depending on the chemical structures and feed ratio of the inorganic acid salt of monoallylamine and the diallylamine derivative used, but usually said initiator is added in an amount of 0.2 to 10% by weight, preferably 1 to 5% by weight, based on the monomer.
• T hhe polymerization temperature is also variable depending on the chemical structure of the initiator used, but it is in the range of 30 to 100°C, usually 45 to 85°C.
• the polymerization according to this invention is usually conducted in the air, but since the polymerization is somewhat affected by oxygen in the air, it is desirable, though not essential, to carry out the polymerization in an inert gas such as nitrogen. Also, the polymerization according to this invention can be conducted either in a stationary state or under stirring.
• the present invention features the use of a radical initiator containing an azo group and a group having cationic nitrogen atom in the molecule for polymerizing an inorganic acid salt of monoallylamine and a diallylamine derivative in a polar solvent and is typified by the fact that, owing to the use of said radical initiator, said monomers can be copolymerized very easily in a desired ratio, allowing obtainment of the desired copolymer with a high degree of polymerization in a high yield.
• the monoallylamine (hereinafter abbreviated as MAA) used as a starting material was the following preparation: MAA produced by Shell Chemical Co., U.S.A., was dried over granular sodium hydroxide and fractionated under nitrogen and the fraction with a boiling point of 52.5 - 53.0°C was used as said starting MAA.
• MAA monoallylamine
• This fraction as its gas chromatographic analysis showed, contained no diallylamine and triallylamine.
• DAA diallylamine
• DAA diallylamine
• DAA diallylamine produced by Shell Chemical Co. was dried over granular sodium hydroxide and fractionated under nitrogen and the fraction with a boiling point of 111 - 112°C was used as starting DAA.
• the gas chromatographic analysis of this fraction showed that it contained no monoallylamine and triallylamine.
• MAA ⁇ HC1 MAA hydrochloride
• DAA ⁇ HCl DAA hydrochloride
• MAA ⁇ HCl was prepared by adding dropwise 571 g (10 mol) of MAA into 1.1 kg of concentrated hydrochloric acid (35% by weight) under stirring and ice cooling at 5 - 20°C and subjecting the reaction mixture to a concentration treatment under reduced pressure by using a rotary evaporator to remove water and excess hydrogen chloride to thereby obtain a 75% by weight aqueous solution of MAA ⁇ HCl.
• DAA.HC1 was prepared by adding dropwise 972 g (10 mol) of DAA into 1.1 kg of concentrated hydrochloric acid (35% by weight) under stirring and ice cooling at 5 - 30°C and subjecting the reaction mixture to a concentration treatment under reduced pressure by using a rotary evaporator to remove water and excess hydrogen chloride to thereby obtain a 70 wt.% aqueous solution of MAA.HC1.
• the thus synthesized monomers were fed into a separable flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet in the molar ratios shown in Table 1. Nitrogen gas was blown through the solution under heating at 65°C to effect nitrogen substitution. Then 2,2'-diamidinyl-2,2'-azopropane hydrochloride in an amount of 2.5% by weight to the total weight of monomers was added in the form of a 15% by weight aqueous solution in five portions at intervals of about 3 hours. Generation of heat and foaming occured with the addition of the initiator and the solution became viscous gradually with the lapse of time. After the final addition of the initiator, the solution was heated to 75°C and further stirred for about 3 hours to complete the polymerization.
• the polymerization was carried out by using as initiator a 25% by weight aqueous solution of ammonium persulfate in an amount of 3% by weight to the total weight of monomers (the initiator being added in six 0.5% by weight portions) under otherwise the same conditions as described above.
• the polymerization conditions, yield and intrinsic viscosity of the resulting products are also shown in Table 1 as Comparative Examples 1-4.
• MAA ⁇ HCl was synthesized in the manner described in Examples 1-4 while MDAA-HCQ was synthesized in the following way: 1,112 g (10 mol) of methyldiallylamine was added dropwise into 1.1 kg of concentrated hydrochloric acid (35% by weight) under stirring and ice cooling at 5 - 30°C and the reaction mixture was subjected to a concentration treatment by using a rotary evaporator to remove water and excess hydrogen chloride, thereby obtaining a 75% by weight aqueous solution of DMAA ⁇ HCl.
• the thus obtained monomers were polymerized by using the same polymerization apparatus under the same polymerization conditions as used in Examples 1-4 and further subjected to the same treatment as in Examples 1-4 to obtain a yellowish white powdery copolymer. A part of this copolymer product was sampled and its yield and intrinsic viscosity (in N/10 NaCi at 30°C) were determined.
• Example 5 where 2,2'- diamidinyl-2,2'-azopropane hydrochloride was used as polymerization initiator shows higher yield and intrinsic viscosity than Comparative Example 5 where APS was used as polymerization initiator.
• MAA ⁇ HCl was synthesized according to the method of Examples 1-4.
• DMDAAmCk was synthesized in the following way. 902 g (10 mol) of a 50% aqueous solution of dimethylamine was fed into a separable flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and then 1,531 g (20 mol) of allyl chloride was added thereto under stirring from the dropping funnel over a period of 7 hours. 1.5 hour after the start of dropwise addition of allyl chloride, 800 g (10 mol) of a 50% aqueous solution of sodium hydroxide was added from the dropping funnel over a period of 5.5 hours.
• the temperature was maintained at 30°C for the first 5-hour period and then gradually raised still reaching 45°C at the termination of the dropwise addition. Thereafter the temperature was further raised to 50°C and the reaction was carried out at this temperature for 10 hours: The reaction mixture was subjected to a concentration treatment with a rotary evaporator, and water and precipitated sodium chloride were filtered out to obtain a 65% aqueous solution of DMDAAmCl.
• Table 3 shows that in case of using 2,2'- diamidinyl-2,2'-azopropane hydrochloride as polymerization initiator, there can be obtained the desired copolymer with a higher degree of polymerization in a higher yield than when using APS as polymerization initiator as in Comparative Examples 6-7.
• the monomers used in the present examples were synthesized in the following ways.
• For preparing MAA ⁇ H 3 PO 4 571 g (10 mol) of MAA was added dropwise with care into a mixed solution of 1,153 g (10 mol) of concentrated phosphoric acid (85% by weight) and 861 g of water under stirring.
• white crystals of MAA ⁇ H 3 PO 4 separated out and the whole reaction system became a slurry, making it hard conduct stirring and cooling.
• the slurry-like solution was heated at 50 - 55°C and further stirred for about one hour to obtain a colorless and transparent viscous 60% aqueous solution of MAA ⁇ H 3 PO 4 .
• DAA ⁇ H 3 PO 4 was prepared by adding dropwise 972 g (10 mol) of DAA into a mixed solution of 1,153 g (10 mol) of concentrated phosphoric acid (85% by weight) and 878 g of water under stirring and ice cooling at 10 - 30°C, heating the reaction mixture at 50 - 55°C and stirring it for about one hour to obtain a light-yellow transparent 65% aqueous solution of DAA ⁇ H 3 PO 4 .
• MDAA ⁇ H 3 PO 4 was prepared by adding dropwise 1,112 g (10 mol) of MDAA into a mixed solution of 1,153 g (10 mol) of concentrated phosphoric acid (85% by weight) and 954 g of water under stirring and ice cooling at 10 - 30°C, heating the reaction mixture at 50 - 55°C and stirring it for about one hour to obtan yellow transparent 65% aqueous solution of MDAA ⁇ H 3 PO 4 .
• DMDAAmCk was synthesized by the method used in Examples 6-7.
• the thus synthesized monomers were polymerized by using the same polymerization apparatus and under the same polymerization conditions as explained in Examples 1-4 and further subjected to the same treatment as in Examples 1-4.
• the resulting copolymers were sampled and their yield and intrinsic vissocisty were determined.
• the polymerization was carried out in the same way as Examples 1-10 except for use of 2,2'-bis-(N-phenyl- amidinyl)-2,2'-azopropane hydrochloride in place of 2,2'- diamidinyl-2,2'-azopropane hydrochloride as polymerization initiator.
• 2,2'-bis-(N-phenyl- amidinyl)-2,2'-azopropane hydrochloride in place of 2,2'- diamidinyl-2,2'-azopropane hydrochloride as polymerization initiator.
• the yield was 100% and the intrinsic viscosity (at 30°C in N/10 NaCk) was 0.61.
• the polymerization was carried out according to the process of Examples 1-10 except for use of 2,2'-azobis-(2-(imidazolynyl)propane) hydrochloride in palce of 2,2'-diamidinyl-2,2'-azopropane hydrochloride as polymerization initiator, and thereafter the same operations as in Examples 1-4 were repeated to obtain a white powdery copolymer.
• the yield was 98.2% and the intrinsic viscosity (at 30°C in N/10 NaCl) was 0.63.

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• 1983
  • 1983-10-21 JP JP58197112A patent/JPS6088018A/ja active Granted
• 1984
  • 1984-10-19 DE DE8484112652T patent/DE3474674D1/de not_active Expired
  • 1984-10-19 AU AU34490/84A patent/AU552740B2/en not_active Expired
  • 1984-10-19 EP EP84112652A patent/EP0140309B1/de not_active Expired
• 1987
  • 1987-05-12 US US07/051,181 patent/US4812540A/en not_active Expired - Lifetime

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